循环冲击载荷作用下页岩动力学响应及能量耗散特征

采用$\varnothing $50 mm分离式霍普金森杆(split Hopkinson pressure bar,SHPB)实验系统开展页岩循环冲击实验,研究不同循环冲击载荷作用下页岩动力学响应及损伤演化特征,同时揭示了控制入射总能量不变条件下,不同气压梯度循环冲击页岩能量演化规律。随着冲击气压升高,试样破裂所需的冲击次数呈线性减少,峰值应力随循环冲击次数的增加先升高后降低,极限应变先减小后增大,试样在循环冲击下表现出先压密后损伤的力学机制。基于Weibull分布的统计损伤模型表明,升高循环冲击气压,试样损伤破坏形式由缓慢劣化逐渐转变为骤然破坏。入射总能量恒定的情况下,通过控制循环入射能量梯度能够产生不同的损伤效果,降压冲击和升压冲击下的能量吸收比均大于恒压冲击下的,且气压梯度的绝对值与能量吸收比呈现正相关性。

     

CO2-水-页岩相互作用的研究现状及展望

简要综述了CO2、水和页岩间矿物的相互作用,分析了CO2注入到地下进入页岩层后,地下含水层pH值的变化,并根据页岩层的矿物学组成分为黏土矿物和脆性矿物,较为详细地描述了CO2与黏土矿物和脆性矿物之间发生的地球化学反应,概述了此反应对页岩层孔隙度和渗透率的影响。同时,也讨论了CO2增强页岩气开采的现实问题及发展趋势,为今后的研究提供了参考。     

Postdiagenetic Changes in Kerogen Properties and Type by Bacterial Oxidation and Dehydrogenation

A significant part of organic carbon found on the earth is deposited as fossil organic matter in the lithosphere. The most important reservoir of carbon is shale rocks enriched with organic matter in the form of kerogen created during diagenesis. The purpose of this study was to analyze whether the bacterial communities currently inhabiting the shale rocks have had any impact on the properties and type of kerogen. We used the shale rock located on the Fore-Sudetic Monocline, which is characterized by oil-prone kerogen type II. We were able to show that shale rock inhabited by bacterial communities are characterized by oxidized and dehydrated kerogen type III (gas-prone) and type IV (nonproductive, residual, and hydrogen-free). Bacterial communities inhabiting shale rock were dominated by heterotrophs of the Proteobacteria, Firmicutes, and Actinobacteria phyla. Additionally, we detected a number of protein sequences in the metaproteomes of bacterial communities matched with enzymes involved in the oxidative metabolism of aliphatic and aromatic hydrocarbons, which may potentially contribute to the postdiagenetic oxidation and dehydrogenation of kerogen. The kerogen transformation contributes to the mobilization of fossil carbon in the form of extractable bitumen dominated by oxidized organic compounds.     

Heating rate effect on the DSC kinetics of oil shales

This research was aimed to investigate the combustion and kinetics of oil shale samples (Mengen and Himmetoğlu) by differential scanning calorimetry (DSC). Experiments were performed in air atmosphere up to 600°C at five different heating rates. The DSC curves clearly demonstrate distinct reaction regions in the oil shale samples studied. Reaction intervals, peak and burn-out temperatures of the oil shale samples are also determined. Arrhenius kinetic method was used to analyze the DSC data and it was observed that the activation energies of the samples are varied in the range of 22.4–127.3 kJ mol⁻¹ depending on the oil shale type and heating rate.     

Evaluation of Oil Yield of Oil Shale by Infrared Spectrometry Coupled with Ultrasound-assisted Extraction

The oil yield of oil shale was evaluated by Fourier transform infrared(FTIR) spectrometry coupled with ultrasound-assisted extraction. The extraction conditions, including the amount of sample, extraction time and extraction temperature, were examined and optimized. Twenty-four oil shale samples were collected and divided into calibration set and prediction set randomly with a ratio of 2:1. The oil yields of all the samples were determined by the routine method(low-temperature retorting) for reference. The linear regression(LR) equations of oil yield vs. the total area of the spectrum peaks in a wavenumber range of 3100-2800 cm^-1 as well as the sum of absorbance of three absorption peaks(2855, 2927 and 2955 cm^-1), and the multiple linear regression(MLR) model of oil yield vs. the absorbances of the three absorption peaks were constructed with the samples in calibration set and applied to the evaluation of the oil yields of the samples in prediction set, respectively. The results show that the MLR model provides more accurate predictions than the other LR two equations. The determination coefficient(R_p²), the root-mean-square error of prediction(RMSEP) and the residual prediction deviation(RPD) of the MLR model are 0.9616, 0.6458 and 3.6, respectively. The present method is a rapid and effective alternative to the routine low-temperature retorting method.     

抚顺页岩油的高分辨核磁共振研究

用高分辨液体核磁共振氢谱、碳谱、二维碳氢相关谱和DEPT谱(无畸变极化转移增强法)对我国抚顺页岩油的不同组分进行了详细研究,得出了一些结构信息和变化规律。     

The role of MgO in the binding of SO<Subscript>2 </Subscript>by lime-containing materials

Summary The results of investigation of MgO participation in the binding of SO₂ with lime-containing materials as sorbents are presented. Experiments of SO₂ binding into solid phase using model samples of reactive grade MgO and CaO varying the mole ratio of MgO/CaO from 9:1 to 1:9 were carried out. Besides, dolomite and limestone samples with different MgO/CaO mole ratio (from 1.24 to 0.13) and samples of ashes formed at combustion of Estonian oil shale (containing 35-40% of carbonates) and its semicoke were studied Initial samples, intermediate and final products were subjected to chemical, IR-spectroscopy, X-ray and BET specific surface area analyses. The results of the present study confirmed the active participation of MgO in the binding of SO₂ into the solid phase. In addition to CaSO₄ the formation of Ca,Mg-double sulphate CaMg₃(SO₄)₄ and -MgSO₄ was observed. The presence of CaMg₃(SO₄)₄ was fixed in a large temperature range 400-900°C and that of -MgSO₄ in between 500-700°C. The optimum temperature range for formation and durability of CaMg₃(SO₄)₄ was 700-800°C.     

基于低场核磁共振的抚顺油页岩孔隙连通性演化研究

油页岩原位注热开采过程中，储层内部孔隙结构的连通性直接影响载热介质的流动行为和传热效率，同时对油气产物的扩散和流动行为起控制作用.本文利用低场核磁共振（LF NMR）技术，考察了不同热解终温（23~650℃）处理时，饱和水及束缚水状态下抚顺油页岩的T₂谱，分析了可动流体T₂截止值、束缚流体孔隙度、饱和流体孔隙度、渗透率等NMR孔隙参数，定量研究了随热解终温升高，抚顺油页岩孔隙结构的连通性演化规律.研究结果表明热解终温对抚顺油页岩孔隙连通性及渗透率的变化起控制作用，且可动流体孔隙度对总孔隙度的增加起主要促进作用，这说明热解终温升高加大了渗透率及油气产物的输运能力.本文为深入认识油页岩原位热解过程中孔隙结构的演化提供了依据.     

Applicability of equilibrium and kinetic models on the herbicide 4-chloro-2-methyl phenoxyacetic acid adsorption on bituminous shale

Adsorption characteristics of herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) have been evaluated using bituminous shale (BS) as a model adsorbent-containing solid organic matter in a mineral matrix. The adsorption of MCPA on BS has been studied with varying concentration, temperature, pH and contact time, using batch technique. Adsorption ability of BS increases with increasing temperature and decreasing pH in the studied concentration range of (0.6–4.0) × 10⁻⁴ M. Theoretical curves calculated from Freundlich, Dubinin-Radushkevich (D-R), Langmuir and Temkin isotherm equations show a two-step isotherm shape. The results could be explained by assuming the presence of two-type sites with different affinity on adsorbent surface. Adsorption process is endothermic and entropy controlled at the first stage, and exothermic and enthalpy controlled at the second stage. The mechanism proposed based on surface ionization and complexation model is consistent with the pH dependent experimental results. Kinetic data fit well to both Paterson’s and Nernst Planck model based on homogeneous solid phase diffusion (HSPD). The values of particle diffusion coefficients (D _p ) predicted from both models are comparable each other and independent of temperature and concentration.      

基于扩展有限元的页岩水平井多裂缝模拟研究

页岩储层水平井分段多簇压裂簇间距优选是压裂技术的关键,建立了水力压裂流固耦合数学模型,基于扩展有限单元法模拟多条裂缝的扩展过程,研究多条裂缝同时扩展的转向规律,以及应力干扰、水平主应力差、裂缝间距等因素与裂缝转向角度的关系.结果表明:应力干扰作用对裂缝宽度具有限制作用,单条裂缝张开宽度比两条裂缝的大;裂缝转角随应力差的减小而增大,随压裂时间的增加而增大.簇间距越小,应力干扰越强,转角越大,综合主缝均匀扩展、支撑剂填充以及复杂裂缝网络形成等条件,确定最优簇间距为30~40 m.多条裂缝同时扩展时,中间裂缝会受到两边裂缝的限制作用,簇间距越小,限制作用越强,裂缝发育时间越长,扩展速度越慢.